Synthesis of silirenes by palladium-catalyzed transfer of silylene from siliranes to alkynes

Organometallics

Volumn 16, Issue 22, 1997, Pages 4824-4827

  Palmer, Wylie S ^a   Woerpel, K A ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000999374     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om9704861     Document Type: Article

References (29)

1. Tamao, K.; Sun, G.-R.; Kawachi, A. J. Am. Chem. Soc. 1995, 117, 8043-8044.
2. Yamamoto, K.; Okinoshima, H.; Kumada, M. J. Organomet. Chem. 1971, 27, C31-C32.
3. Tamao, K.; Tarao, Y.; Nakagawa, Y.; Nagata, K.; Ito, Y. Organometallics 1993, 12, 1113-1120.
4. Palmer, W. S.; Woerpel, K. A. Organometallics 1997, 16, 1097-1099.
5. Ishikawa, M.; Sugisawa, H.; Harata, O.; Kumada, M. J. Organomet. Chem. 1981, 217, 43-50.
6. Okinoshima, H.; Yamamoto, K.; Kumada, M. J. Am. Chem. Soc. 1972, 94, 9263-9264.
7. Ishikawa, M.; Fuchikami, T.; Kumada, M. J. Chem. Soc., Chem. Commun. 1977, 352.
8. Boudjouk, P.; Samaraweera, U.; Sooriyakumaran, R.; Chrusciel, J.; Anderson, K. R. Angew. Chem., Int. Ed. Engl. 1988, 27, 1355-1356.
9. Ohshita and Ishikawa demonstrated an equilibrium between two silirenes in the presence of an alkyne, although silirene products were not isolated, see: Ohshita, J.; Ishikawa, M. J. Organomet. Chem. 1991, 407, 157-165.
10. Pyrolysis of 1,2-dimethoxy-1,1,2,2-tetramethyldisilane with 2-butyne afforded a stable silirene, although this synthesis provided mixtures of products, see: Conlin, R. T.; Gaspar, P. P. J. Am. Chem. Soc. 1976, 98, 3715-3716.
11. The first silirenes that could be isolated in pure form and fully characterized were prepared by Seyferth. The synthesis involved thermal silylene transfer from a silirane to an alkyne, see: (a) Seyferth, D.; Annarelli, D. C.; Vick, S. C. J. Am. Chem. Soc. 1976, 98, 6382-6384. (b) Seyferth, D.; Annarelli, D. C.; Vick, S. C. J. Organomet. Chem. 1984, 272, 123-139.
12. The first silirenes that could be isolated in pure form and fully characterized were prepared by Seyferth. The synthesis involved thermal silylene transfer from a silirane to an alkyne, see: (a) Seyferth, D.; Annarelli, D. C.; Vick, S. C. J. Am. Chem. Soc. 1976, 98, 6382-6384. (b) Seyferth, D.; Annarelli, D. C.; Vick, S. C. J. Organomet. Chem. 1984, 272, 123-139.
13. For other examples of silirene syntheses using thermal and photochemical methods, see: (a) Sakurai, H.; Kamiyama, Y.; Nakadaira, Y. J. Am. Chem. Soc. 1977, 99, 3879-3880. (b) Reference 8. (c) Belzner, J.; Ihmels, H. Tetrahedron Lett. 1993, 34, 6541-6544. (d) Ando, W.; Shiba, T.; Hidaka, T.; Morihashi, K.; Kikuchi, O. J. Am. Chem. Soc. 1997, 119, 3629-3630.
14. For other examples of silirene syntheses using thermal and photochemical methods, see: (a) Sakurai, H.; Kamiyama, Y.; Nakadaira, Y. J. Am. Chem. Soc. 1977, 99, 3879-3880. (b) Reference 8. (c) Belzner, J.; Ihmels, H. Tetrahedron Lett. 1993, 34, 6541-6544. (d) Ando, W.; Shiba, T.; Hidaka, T.; Morihashi, K.; Kikuchi, O. J. Am. Chem. Soc. 1997, 119, 3629-3630.
15. For other examples of silirene syntheses using thermal and photochemical methods, see: (a) Sakurai, H.; Kamiyama, Y.; Nakadaira, Y. J. Am. Chem. Soc. 1977, 99, 3879-3880. (b) Reference 8. (c) Belzner, J.; Ihmels, H. Tetrahedron Lett. 1993, 34, 6541-6544. (d) Ando, W.; Shiba, T.; Hidaka, T.; Morihashi, K.; Kikuchi, O. J. Am. Chem. Soc. 1997, 119, 3629-3630.
16. For other examples of silirene syntheses using thermal and photochemical methods, see: (a) Sakurai, H.; Kamiyama, Y.; Nakadaira, Y. J. Am. Chem. Soc. 1977, 99, 3879-3880. (b) Reference 8. (c) Belzner, J.; Ihmels, H. Tetrahedron Lett. 1993, 34, 6541-6544. (d) Ando, W.; Shiba, T.; Hidaka, T.; Morihashi, K.; Kikuchi, O. J. Am. Chem. Soc. 1997, 119, 3629-3630.
17. For example, metal-mediated cyclopropane synthesis has been well-investigated, see: Brookhart, M.; Studebaker, W. B. Chem. Rev. 1987, 87, 411-432.
18. 3 substituents appear to increase the shielding of the ringbearing silicon atom, hence this chemical shift would be consistent with data reported in Table 1. See ref 8.
19. The regiochemistry indicated for 6c was indicated by a 12% NOB between the tert-butyl group and the hydrogen on the ring.
20. Control experiments where 5c and 5d were treated with phenylacetylene in the absence of palladium gave only unidentifiable degradation products.
21. Seyferth, D.; Shannon, M. L.; Vick, S. C.; Lim, T. F. O. Organometallics 1985, 4, 57-62.
22. Ishikawa, M.; Sugisawa, H.; Kumada, M.; Higuchi, T.; Matsui, K.; Hirotsu, K. Organometallics 1982, 1, 1473-1477.
23. A related nickelasilacyclobutene has been observed, see: Ishikawa, M.; Ohshita, J.; Ito, Y.; Iyoda, J. J. Am. Chem. Soc. 1986, 108, 7417-7419.
24. A platinasilacyclohexadiene has been characterized and shown to reductively eliminate to form a silole, see: Yamashita, H.; Tanaka, M.; Goto, M. Organometallics 1992, 11, 3227-3232.
25. Goller, A.; Heydt, H.; Clark, T. J. Org. Chem. 1996, 61, 5840-5846.
26. Wild has recently reported the reaction of a phosphiranium ion with an alkyne to afford a phosphirenium ion, see: Hockless, D. C. R.; McDonald, M. A.; Pabel, M.; Wild, S. B. J. Organomet. Chem. 1997, 529, 189-196.
27. The alkyne was thermally unstable and readily formed 1-(tertbutyldimethyl)silyl-2-butyn-1-oI.
28. Repeated attempts to obtain satisfactory elemental analysis failed.
29. 6 was confirmed by a DEPT experiment.